Azo dyestuffs and their manufacture



Patented May 16, 1939 AZO DYESTUFFS AND THEIR MANUFACTURE AchilleConzetti, Basel, Switzerland, assignor to the firm J. R.

Geigy S. A., Basel, Switzerland N Drawing. Application March 12, 1938,Serial No. 195,659. In Switzerland March 19, 1937 9Claims. (Cl.:260193)I inventionrelates to the production of azo dyestufis by, means of,hydro ar'omatic Y. carboeyclidB-diketones; and hasfo'r its object toproduce azo dyestufis having good fastness properties. I

Hydro-aromatic carbocyclic p-diketones with an enolisable keto grou asfor example 5,6- dihydro-L3-dihydroxyben2ene' and its derivatives havealready been used for the production of azo dyestuffs.

In British Patent No. 461,965 it is proposed to combine 5,6-dihydro-1,3dihydroxy-benzene or its derivatives with diazo'compoundsof'amines'containing nitro groups, which in the o-position to as aminogroup do "not contain any carboxylic acid-, carboxylic acid ester-,hydroxy-; alkoxy-, or O-acyl-group, into new dyestufis. These aresuitable for dyeing cellulose derivatives and artificial masses, in sofar as they do not contain any water solubilising groups, whilst thedyestufi's with sulphonic acid groups are suitable for dyeing wool,paper, silk or viscose artificial silk or for the production of calciumor barium lakes.

In United States Patent No. 2,088,911 there is .deseribedj.theproduction of dyestufis, capable of being chromed, from5,6-dihydro-1,3-dihydroxybenzene or its derivatives and diazo compoundsof amines, which in the o-position to .the amino group contain acarboxylic acid-, carboxylic acid ester-, hydroxy-, alkoxyorO-acyl-group.

According to this invention diazo compounds, which are derived fromamino-diand -triphenyl ethers and which containwater solubilising groupsbut no nitro groups, are coupled with hydro-aromatic,carbocyclic-fl-diketones. The diketones should contain an enolisableketo group. Outstanding pure yellow wool and silk 'dyestufis areproduced; which in addition to good fastness to washing and perspirationare also characterised by a very 'good fastness to light. They can alsoserve for the production of lakes by precipitation with alkaline earthsalts.

Example 1 26.5 kg. of 2-amino diphenyl ether-4-sulphonic acid arediazotlsed as usual and the diazo compound lsallowed to run at 0 0. intoa solution of 14.5 kg. of dimethyl dihydro resorcln in 400 litres ofwater and 10 litres of soda lye 29.7% which has been made acid to litmusby the additionof a little dilute acetic acid and to which there havebeen added 20 kg. of. crystallised sbdjium acetate.

b I H The couplingtakesplace very rapidly. Afterstirring for a number ofhours there separates quantitively a "greeny yellow dye.

pent-there may also be used substitution products, such as for exampleand It is filtered and dried. Wool and silk are dyed in an acid bathvery pure greeny yellow shades of very good fastness to light.

Instead of the above mentioned diazo compound there may be used isomeror homologue 5 compounds or their substitution products, for example4-amino diphenyl ether-Z-sulphonic acid or analogous ethers, which canbe substituted by methyl groups and/or halogens, as for example thecompound of the formula (3H3 I m:

produced by. the condensation of 2,4-dichloro-6- methyl-lehydroxybenzene(sodium salt) with .3-'

vnitro -l-chlorobenzene sulphonic acid and sub- Example 2 26.5 kg.4-amino diphenyl ether-3-sulphonic acid are diazotised as usual and thediazo compound is introduced into a solution, acid to litmus, of. 14.5kg. produced according'to the indications in Example 1. After stirringfor several hours the dyestufi' shades of very good fastness to light.

Instead of the above mentioned diazo compol aH ' $0311 The secondcompound can be produced by the condensation of 3,4-di'chloro nltrobenzene with o-cresolate, reduction and sulphonation by the bakingprocess.

I Example 3 35.7 kg. of 1-amino-2,4-diphenyl ether-5-sulphonic acid(produced by reduction of the condensation product of 1 mol.2,4-dichloro-5- .diketohexane-ring maybe used with nitrobenzene--sulphonic acid with 2 mols. of phenolate) are diazotised as usual andthe diazo compound is introduced into a solution of 14.5 kg. dimethyldihydro resorcin dissolved and made acid to litmus as indicated inExample 1. The dyestufi, which separates completely, is filtered anddried. It dyes wool and silk pure yellow shades of very good fastness tolight.

Instead of the above mentioned diazo compoundthere can be usedderivatives thereofwhich are also substituted by methyl groups andhalogen atoms, also compounds of the following type may be used Thistriphenyl ether sulphonic acid is obtained by the condensation of4-hydroxydiphenyl ether (alkali salt) with 3-nitro-4-chlorobenzene sul-'phonic acid and reduction.

;Example 4 29.3 kg. of the amino diphenyl ether sulphoni acid of theformula obtained from 3-nitro-4-chllorobenzene-l-sulphonic acid andm-xylenol (alkali salt) by condensation and ,subsequent reduction, arediazotised as usual and introduced into a fresh suspension precipitatedwith acetic acid of 18.5 kg. of cyclohexane spiro-cyc1ohexane-3,5-dionin 400 --litres.aof-.water .and 19 kg..of crystalline sodium acetate.After stirringior several hours the couplingheatedto 30 C., theseparated dyestufi filtered ofiand dried. It dyeswool and silkyel- -l0wshadesof very good fastness properties.

Instead of the above mentioned diazo compound there may be used thecompounds mentioned in Examples 1 to 3. The dyestuffs obtained possesssimilar properties.

acid

' 1. A process for v dyestuffs onsisting 'in' coupling a diazotisedaminoben'zenesulphonic acid'without nitrogroups substituted in thebenzene nucleus by at least one phenoxy group with 5:6-dihydro-1:3-dihydroxy benzenes.

I 2. A process {or the m uia wr of m nswes'l s ii fi sens e in 9 91 5classes Eng ne a smear e ow .an acid aminodiphenylethe sulphonic acidwithout nitro groups, the diazo group and the phenylether group being inone of the positions ortho and para to each other, with5:6-dihydro-1z3-dihydroxybenzenes.

3. Monoazodyestufis corresponding to the general formula I 1' yvhereintheixfs mean substituents selected from the group consisting of H, Cland CH3 and whereinithe yZs represent a number of 1 and 2 and A when-sinA mean the .radlel b 5161mmfivd h s pxrhe zene l lvl onoazodyestufiscorresponding to .the. 8 :1 erra ema e was wherein :A means the radicalof a 'fizfi-dihydro- -1 :3 -'dihyd-roxybenzene.

6. Monoazodyestuffs corresponding to the general .formula samecqmrf, wterhndfivdns Weeken -si k in hath ye lyrur sme ly-$91. 9! s 9 very. g o9(1v tastnesstq p y 1 U 8. The azo dyestufi of the formula 9. The azodyestufl of the formula bHa & 0=l l o 0 CHa U U i) being a greeny yellowpowder, soluble with the same color in water and dyeing wool and silk inan acid bath very pure greeny yellow shades of I) very good fastness tolight.

ACHILIE CON ZETTI.

